Effect of variation of hydrophobicity of anode diffusion media along the through-plane direction in direct methanol fuel cells

Reducing methanol crossover from the anode to cathode in direct methanol fuel cells (DMFCs) is critical for attaining high cell performance and fuel utilization, particularly when highly concentrated methanol fuel is fed into DMFCs. In this study, we present a novel design of anode diffusion media (DM) wherein spatial variation of hydrophobicity along the through-plane direction is realized by special polytetrafluoroethylene (PTFE) coating procedure. According to the capillary transport theory for porous media, the anode DM design can significantly affect both methanol and water transport processes in DMFCs. To examine its influence, three different membrane-electrode assemblies are fabricated and tested for various methanol feed concentrations. Polarization curves show that cell performance at high methanol feed concentration conditions is greatly improved with the anode DM design with increasing hydrophobicity toward the anode catalyst layer. In addition, we investigate the influence of the wettability of the anode microporous layer (MPL) on cell performance and show that for DMFC operation at high methanol feed concentration, the hydrophilic anode MPL fabricated with an ionomer binder is more beneficial than conventional hydrophobic MPLs fabricated with PTFE. This paper highlights that controlling wetting characteristics of the anode DM and MPL is of paramount importance for mitigating methanol crossover in DMFCs.     

Suppressing methanol crossover with a deposited quaternary Pt-based catalyst on the Nafion surface

A Pt₄₉–Ru₃₅–Ir₆–Os₁₀ alloy layer is deposited on the Nafion membrane surface using the impregnation-reduction (IR) method to mitigate methanol crossover. The methanol crossover in a membrane electrode assembly (MEA) with a deposited Pt–Ru–Ir–Os layer is compared with a MEA without any layer on the proton exchange membrane (PEM). The deposited Pt₄₉–Ru₃₅–Ir₆–Os₁₀ layer functions like a catalytically active layer, a methanol barrier, and an electrode all at the same time. This layer yields up to a 30% suppression of methanol crossover and a 15% improvement in fuel cell voltage performance (@170 mA cm⁻²) at 80 °C. The porous metal alloy layer with a high surface area of the Pt–Ru layer suppresses methanol crossover by the catalytic activity of the deposited layer. The presence of the solid Pt₄₉–Ru₃₅–Ir₆–Os₁₀ layer on the Nafion membrane surface reduces the proton conductivity of the PEM (from 10.75 to 4.22 mS cm⁻¹), and degrades the output of the cell voltage performance (from 0.350 to 0.335 V at 90 mA cm⁻² of current density) at 60 °C, even though methanol crossover is reduced (from 6928 ppm to 4415 ppm (CO₂ concentration at cathode exhaust is proportional to methanol crossover)).     

Hydrogen crossover through perfluorosulfonic acid membranes with variable side chains and its influence in fuel cell lifetime

In this study, hydrogen crossover in long side chain Nafion 211 membrane and short side chain Aquivion membrane is studied under different conditions. It is found that both temperature and relative humidity significantly influence the hydrogen crossover in the polymer electrode membranes (PEMs). The difference in hydrogen crossover behavior between Nafion 211 membrane and Aquivion membrane is revealed. The influence of hydrogen crossover on the fuel cell lifetime is also investigated under open circuit voltage (OCV). It is proved hydrogen crossover in the PEM would lead to possible degradation of the PEM and the decrease of electro-chemical surface area in the catalyst of the single cell. Single cell assembled with Aquivion membrane shows slower OCV and ECSA decay compared to the Nafion 211 single cell. Our results suggest that the PEM fuel cell lifetime is closely related to the hydrogen crossover in the PEM. The current study also highlights the possibility of improving the fuel cell durability by rational design of the PEM morphology.     

求解离散优化问题的元胞量子狼群演化算法

针对离散空间优化问题,提出了求解离散优化问题的元胞量子狼群演化算法,首先,为了提高算法的全局收敛速度,采用双策略量子位初始化方法和滑模交叉方法,分别生成量子狼群初始位置和产生头狼,实现种群多样性;其次,为了描述头狼与猎物间的距离以及增强狼群的遍历范围,采用二进制编码方式和元胞自动机中的演化规则,分别实现狼群中个体狼与猎物距离的精确描述和量子旋转角的选取调整;然后,为了证明该算法的收敛性能,采用泛函分析方法,实现了算法全局收敛性能的验证;最后,通过6个标准测试函数的仿真实验,并与狼群算法以及量子狼群算法的优化结果进行比较。实验结果表明,该算法具有较快的收敛速度和较好的全局寻优能力。     

求解高维优化问题的遗传鸡群优化算法

针对鸡群算法在求解高维复杂优化问题时收敛速度慢、寻优精度不高、容易陷入局部最优等不足,结合遗传思想,增加公鸡和母鸡交配、变异产生新小鸡的概念,并设定交配周期和小鸡淘汰更新周期,利用交叉、变异算子对算法进行改进,得到一种改进的鸡群算法。通过对10组基准函数的实验结果进行分析,相比于标准鸡群算法和其他两种目前比较流行的群体智能优化算法,提出的改进鸡群算法在寻优精度、解的质量、收敛速度、稳定性及鲁棒性等方面优势明显,具有良好的性能。     

Methanol crossover reduction by Nafion modification with palladium composite nanoparticles: Application to direct methanol fuel cells

Modified Nafion membranes by self-assembling of palladium composite nanoparticles were successfully synthesized and used for the reduction of methanol crossover in Direct Methanol Fuel Cells (DMFC). The positively charged polydiallyldimethylammonium (PDDA) was used for stabilizing the palladium nanoparticles. Modified and unmodified membranes were tested in a DMFC at 30 °C and 50 °C. The performance of the DMFC using modified membranes with different composite nanoparticles (i.e., Pd/PDAA ratios) and self-assembling times was compared with that using an unmodified membrane. The modified Nafion membranes proved to reduce the methanol crossover in ca. 10% – 35%, depending on the self-assembling time, nanoparticles composition and test temperature. However, a decrease in the performance was observed mainly for the modified membrane with the higher PDDA content due to a decrease in the proton conductivity. On the other hand, the membrane modified with nanoparticles containing less PDDA and tested at 50 °C showed similar performance as the unmodified one. Additionally, the fuel cell efficiencies obtained for all the modified membranes at both temperatures were similar or higher than the unmodified one.     

Comparison of numerical simulation results with experimental current density and methanol-crossover data for direct methanol fuel cells

The simulation results of a one-dimensional (1D) direct methanol fuel cell (DMFC) model are compared with the current density and methanol-crossover data that are experimentally measured under several different cell designs and operating conditions. No fitting parameters are employed for the comparison and model input parameters obtained from the literature are consistently used for all the cases of comparison. The numerical predictions agree well with the experimental data and the 1D DMFC model successfully captures key experimental trends that are observed in the cell current density and methanol-crossover data. This clearly illustrates that the present DMFC model can be applicable for optimizing DMFC component designs and operating conditions. In addition, the model simulations further indicate that the reduction of the methanol concentration in the anode catalyst layer is critical to simultaneously suppress both the electro-osmotic drag (EOD) and the diffusion aspects of methanol crossover.     

A review on methanol crossover in direct methanol fuel cells: challenges and achievements

Direct methanol fuel cells have the potential to power future microelectronic and portable electronic devices because of their high energy density. One of the major obstacles that currently prevent the widespread applications of direct methanol fuel cells is the methanol crossover through the polymer‐electrolyte membrane. Methanol crossover is closely related to several factors including membrane structure and morphology, membrane thickness, and fuel cell operating conditions such as temperature, pressure, and methanol feed concentration. This work presents a comprehensive overview of the state‐of‐the‐art technology for the most important factors, affecting methanol crossover in direct methanol fuel cells. In addition, the current and future directions of the research and development activities, aiming to reduce the methanol crossover are reviewed and discussed in order to improve the performance of direct methanol fuel cells. Copyright © 2011 John Wiley & Sons, Ltd.     

Completely eliminating the metal barrier cracks on Nafion for suppressing methanol crossover with anodic aluminum oxide substrates

Methanol crossover is one of the main challenges for direct methanol fuel cells (DMFCs). Depositing a metal barrier on Nafion can reduce the crossover but usually faces the metal cracking issues. This study presents a new composite membrane in which an anodic aluminum oxide (AAO) substrate is impregnated with a Nafion solution and then coated with a layer of Au. The AAO/Nafion/Au composite membrane shows an ideal metal crack-free surface. Higher and more stable voltage has been achieved for the cell with the membrane, indicating an effectively suppressed methanol-crossover. Results reveal that there is a tradeoff between suppressing the methanol crossover and increasing the ion transmission. By optimizing the membrane, it can not only suppress the methanol crossover but also enhance the output performance of DMFCs. The current density and power density of the cells can be enhanced by 59% and 52.85%, respectively, compared to the cell with a commercial Nafion 117. Overall, this work provides a new approach to designing crack-free membranes for DMFCs.     

Polyamide-coated Nafion composite membranes with reduced hydrogen crossover produced via interfacial polymerization

Nafion, a perfluoro-sulfonic acid (PFSA)-based polymer, is a promising material that will help realize the commercialization of proton exchange membrane-based fuel cells (PEMFCs) and proton exchange membrane water electrolyzers (PEMWEs). However, Nafion also exhibits reduced mechanical and dimensional stability and increased hydrogen crossover under cell operating conditions in real operational settings, that is, in a hydrated state or in water at 60–80 °C. These factors may negatively affect cell efficiency and durability and thus must be addressed. To overcome these limitations, polyamide-coated Nafion composite membranes were developed for the first time via interfacial polymerization. 3,5-Diaminobenzoic acid (DABA), which contains carboxyl functional groups, was used as a monomer to add hydrophilicity to the membrane, and the coating layer thickness was controlled by adjusting the DABA content. A nanoscale polyamide (PA) layer was coated on the surface of Nafion-212 to fabricate a membrane, PA-c3-Nafion. PA-c3-Nafion was found to show ion conductivity 13.6% higher than that of a pristine Nafion-212 membrane at 80 °C, while providing improved mechanical performance and dimensional stability. In particular, at 95% RH, the hydrogen permeability of PA-c3-Nafion was 16.4% lower than that of Nafion-212 while, in a fully hydrated state, the hydrogen permeability of PA-c3-Nafion was 21.2% lower than that of Nafion-212. The LSV test results also showed that the degree of hydrogen crossover was significantly lower in PA-c3-Nafion than in Nafion-212.